Mesoporous hollow TiO2 shells with controllable crystallinity have been successfully synthesized by using a novel partial etching and re-calcination process. This method involves several sequential preparation steps as follows: 1) Synthesis of SiO2@TiO2@SiO2 colloidal composites through sol–gel processes and crystallization by calcination, 2) partial etching to preferentially remove portions of the SiO2 layers contacting the TiO2 surface, and 3) re-calcination to crystallize the TiO2 and finally etching of the inner and outer SiO2 to produce mesoporous anatase TiO2 shells. The partial etching step produces a small gap between SiO2 and TiO2 layers which allows space for the TiO2 to further grow into large crystal grains. The re-calcination process leads to well developed crystalline TiO2 which maintains the mesoporous shell structure due to the protection of the partially etched outer silica layer. When used as photocatalysts for the degradation of Rhodamine B under UV irradiation, the as-prepared mesoporous TiO2 shells show significantly enhanced catalytic activity. In particular, TiO2 shells synthesized with optimal crystallinity by using this approach show higher performance than commercial P25 TiO2.